JPH0899918A - Hydrofluorinating method for chloro(fluoro)butane - Google Patents
Hydrofluorinating method for chloro(fluoro)butaneInfo
- Publication number
- JPH0899918A JPH0899918A JP7223496A JP22349695A JPH0899918A JP H0899918 A JPH0899918 A JP H0899918A JP 7223496 A JP7223496 A JP 7223496A JP 22349695 A JP22349695 A JP 22349695A JP H0899918 A JPH0899918 A JP H0899918A
- Authority
- JP
- Japan
- Prior art keywords
- chloro
- fluoro
- butane
- group
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、一般式C4 H5 C
lX F5-X (式中、x=1〜5)のクロロ(フルオロ)
ブタンのヒドロフルオロ化(hydrofluorination )法に
関する。また、本発明は、1,1,1,3,3-ペンタフルオロブ
タン調製のための本方法の使用に関する。FIELD OF THE INVENTION The present invention has the general formula C 4 H 5 C
l X F 5-X (where x = 1 to 5) chloro (fluoro)
It relates to a method for hydrofluorination of butane. The invention also relates to the use of the method for the preparation of 1,1,1,3,3-pentafluorobutane.
【0002】[0002]
【従来の技術】マクビー(McBee )ら(Ind. Eng. Che
m.,39巻(1947年)、 420頁)には、酸化第二水銀の存
在下でフッ化水素により1,1,1-トリクロロ−3,3-ジフル
オロブタンをヒドロフルオロ化する1,1,1,3,3-ペンタフ
ルオロブタンの調製法が開示されている。1,1,1,3,3-ペ
ンタフルオロブタンのこの既知の調製法は、1つには酸
化第二水銀を使用するため、また他の理由としてヒドロ
フルオロ化反応の低い収率(15%より低い)のため、
工業化に利用するのが困難である。[Prior Art] McBee et al. (Ind. Eng. Che
m., 39 (1947), p. 420), hydrofluorinates 1,1,1-trichloro-3,3-difluorobutane with hydrogen fluoride in the presence of mercuric oxide. A method of preparing 1,1,3,3-pentafluorobutane is disclosed. This known method for the preparation of 1,1,1,3,3-pentafluorobutane uses mercuric oxide as one of the other reasons, and for other reasons it has a low yield of the hydrofluorination reaction (15%). Lower)
It is difficult to use for industrialization.
【0003】[0003]
【発明が解決しようとする課題】本発明の目的は、一般
式C4 H5 ClX F5-X (式中、x=1〜5)のクロロ
(フルオロ)ブタンのヒドロフルオロ化を提供すること
にあり、上記の不都合を避け、工業化に利用するのに簡
便であり、高収率のヒドロフルオロ化とともに、さらに
高い度合いでフッ素化(fluorination)を達成できるよ
うにすることにある。The object of the present invention is to provide the hydrofluorination of chloro (fluoro) butanes of the general formula C 4 H 5 Cl X F 5-X , where x = 1-5. In particular, it is to avoid the above-mentioned inconveniences, be simple to use for industrialization, and to achieve a high yield of hydrofluorination and also to achieve a higher degree of fluorination.
【0004】[0004]
【課題を解決するための手段】この目的のため、本発明
は、周期表IIIa族、 IVa族、 IVb族、Va族、Vb族、及び
VIb族元素の金属の誘導体から選ばれる触媒の存在下
で、フッ化水素を用いる、一般式C4 H5 ClX F5-X
(式中、x=1〜5)のクロロ(フルオロ)ブタンのヒ
ドロフルオロ化法に関する。本発明の方法において、ク
ロロ(フルオロ)ブタンの語は、一般式C4 H5 ClX
F5-X (式中、x=1〜5)の線状及び分岐状化合物す
べてを意味するものである。クロロ(フルオロ)ブタン
の語には、したがって、ペンタクロロブタン、上記の式
のクロロフルオロブタン、及びこれらの化合物の2以上
の混合物も組み込まれる。To this end, the present invention provides a periodic table of groups IIIa, IVa, IVb, Va, Vb, and
A compound of the general formula C 4 H 5 Cl X F 5-X using hydrogen fluoride in the presence of a catalyst selected from the group VIb group metal derivatives.
(Wherein x = 1-5) and relates to a hydrofluorination method of chloro (fluoro) butane. In the process of the present invention, the term chloro (fluoro) butane has the general formula C 4 H 5 Cl x
It means all the linear and branched compounds of F 5-X (wherein x = 1 to 5). The term chloro (fluoro) butane thus also includes pentachlorobutane, chlorofluorobutanes of the above formula, and mixtures of two or more of these compounds.
【0005】[0005]
【発明の実施の形態】本発明の方法のある特定の態様に
おいて、クロロ(フルオロ)ブタンは一般式CH3-CC
lx F2-x - CH2-CCly F3-y (式中、x=0、
1、又は2であり、y=0、1、2、又は3であり、か
つx+y≧1である)の化合物から選ばれる。この態様
において、クロロ(フルオロ)ブタンには、特に1,1,1,
3,3-ペンタフルオロブタンCH3-CCl2-CH2-CCl
3 、又は次のさまざまなクロロフルオロブタンを挙げる
ことができる。CH3-CCl2-CH2-CCl2 F、CH
3-CCl2-CH2-CClF2 、CH3-CCl2-CH2-C
F3 、CH3-CClF- CH2-CCl3 、CH3-CCl
F- CH2-CCl2 F、CH3-CClF- CH2-CCl
F2 、CH3-CClF- CH2-CF3 、CH3-CF2-C
H2-CCl3 、CH 3-CF2-CH2-CCl2 F、CH3-
CF2-CH2-CClF2 、及びこれらの化合物それぞれ
との混合物である。本方法のこの特定の態様の第1の変
形によると、クロロ(フルオロ)ブタンは1,1,3,3-テト
ラフルオロ−1-クロロブタン、1,3,3-トリフルオロ−1,
1-ジクロロブタン、及び1,1,3-トリフルオロ−1,3-ジク
ロロブタンから選ばれる。DETAILED DESCRIPTION OF THE INVENTION In one particular aspect of the method of the invention,
Chloro (fluoro) butane has the general formula CH3-CC
lxF2-x-CH2-CClyF3-y(Where x = 0,
1 or 2 and y = 0, 1, 2, or 3, or
X + y ≧ 1). This aspect
In chloro (fluoro) butane, especially 1,1,1,1
3,3-Pentafluorobutane CH3-CCl2-CH2-CCl
3, Or the following various chlorofluorobutanes
be able to. CH3-CCl2-CH2-CCl2F, CH
3-CCl2-CH2-CClF2, CH3-CCl2-CH2-C
F3, CH3-CClF- CH2-CCl3, CH3-CCl
F-CH2-CCl2F, CH3-CClF- CH2-CCl
F2, CH3-CClF- CH2-CF3, CH3-CF2-C
H2-CCl3, CH 3-CF2-CH2-CCl2F, CH3-
CF2-CH2-CClF2, And each of these compounds
It is a mixture with. A first variation of this particular aspect of the method
According to the form, chloro (fluoro) butane is 1,1,3,3-teto
Rafluoro-1-chlorobutane, 1,3,3-trifluoro-1,
1-dichlorobutane, and 1,1,3-trifluoro-1,3-dic
Selected from lorobutane.
【0006】本発明の方法のこの特定の態様の他の変形
によると、塩化ビニリデンをフッ化水素と反応させるこ
とにより得られたクロロ(フルオロ)ブタン、例えば1-
クロロ−1,1-ジフルオロエタン及び/又は1,1-ジクロロ
−1-フルオロエタンの工業製品の副生成物に使用でき
る。本発明の態様のこの変形において、クロロ(フルオ
ロ)ブタンは、1,1-ジクロロ−1-フルオロエタン、1,1,
1-トリクロロエタンのような他の塩素化又はクロロフル
オロ化副生成物、及び塩素化又はクロロフルオロ化ヘキ
サンを含むことができる。これらの不純物は、本発明の
方法の進行を著しく妨害せず、得られた反応生成物から
後に分離することができる。According to another variant of this particular embodiment of the process according to the invention, a chloro (fluoro) butane obtained by reacting vinylidene chloride with hydrogen fluoride, for example 1-
It can be used as a by-product of industrial products of chloro-1,1-difluoroethane and / or 1,1-dichloro-1-fluoroethane. In this variant of the embodiment of the invention, chloro (fluoro) butane is 1,1-dichloro-1-fluoroethane, 1,1,
Other chlorinated or chlorofluorinated byproducts such as 1-trichloroethane, and chlorinated or chlorofluorinated hexanes can be included. These impurities do not significantly hinder the progress of the process according to the invention and can be subsequently separated from the reaction products obtained.
【0007】本発明の方法において、触媒は周期表IIIa
族、 IVa族、 IVb族、Va族、Vb族、及び VIb族元素の金
属の誘導体から選ばれる。周期表IIIa族、 IVa族、 IVb
族、Va族、Vb族、及び VIb族元素の金属の誘導体は、水
酸化物、酸化物、並びにこれらの金属の有機及び無機
塩、並びにこれらの混合物を意味している。触媒は、好
ましくは周期表 IVa族及びVa族元素の金属の誘導体から
選ばれ、特にスズ及びアンチモンの誘導体から選ばれる
のが好ましい。本発明の方法において、周期表IIIa族、
IVa族、 IVb族、Va族、Vb族、及び VIb族元素の金属の
誘導体は、塩が好ましく、これらはハロゲン化物から選
ばれるのが好ましく、特に塩化物、フッ化物、及びクロ
ロフルオロ化物から選ばれるのが好ましい。本発明によ
り特に好ましい触媒は、スズ及びアンチモンの塩化物、
フッ化物、クロロフルオロ化物であり、特に四塩化スズ
及び五塩化アンチモンが好ましい。五塩化アンチモンは
特に好ましい。用いる触媒の量は、広範囲に変化するこ
とができる。一般に、クロロ(フルオロ)ブタン1モル
当り、触媒を少なくとも0.001モルとする。クロロ
(フルオロ)ブタン1モル当り、触媒を少なくとも0.
01モルとするのが好ましい。多くの場合、用いる触媒
の量は、クロロ(フルオロ)ブタン1モル当り、1モル
を越えない。クロロ(フルオロ)ブタン1モル当り、触
媒0.1モルを越えないのが好ましい。In the process of the present invention, the catalyst is Periodic Table IIIa.
It is selected from the metal derivatives of Group IVa, IVa, IVb, Va, Vb, and VIb elements. Periodic Table IIIa, IVa, IVb
Derivatives of metals of Group Va, Va, Vb, and VIb elements mean hydroxides, oxides, and organic and inorganic salts of these metals, and mixtures thereof. The catalyst is preferably selected from derivatives of metals of Group IVa and Va elements of the Periodic Table, especially from derivatives of tin and antimony. In the method of the present invention, Group IIIa of the periodic table,
The metal derivative of the IVa group, IVb group, Va group, Vb group, and VIb group element is preferably a salt, and these are preferably selected from halides, particularly chloride, fluoride, and chlorofluoride. Preferably. Particularly preferred catalysts according to the invention are tin and antimony chlorides,
Fluoride and chlorofluoride, and tin tetrachloride and antimony pentachloride are particularly preferable. Antimony pentachloride is particularly preferred. The amount of catalyst used can vary within wide limits. Generally, there is at least 0.001 mole of catalyst per mole of chloro (fluoro) butane. The catalyst is at least 0.5 per mole of chloro (fluoro) butane.
It is preferably set to 01 mol. In many cases, the amount of catalyst used does not exceed 1 mol per mol of chloro (fluoro) butane. It is preferred not to exceed 0.1 mol of catalyst per mol of chloro (fluoro) butane.
【0008】用いるクロロ(フルオロ)ブタンに対する
フッ化水素のモル比は、一般に少なくとも4である。こ
の作用は、モル比を少なくとも8で行うのが好ましい。
用いるクロロ(フルオロ)ブタンに対するフッ化水素の
モル比は、一般に25を越えない。好ましくは、モル比
は18を越えるべきではない。ヒドロフルオロ化が行わ
れる温度は、一般に少なくとも50℃である。少なくと
も80℃であるのが好ましい。温度は一般に150℃を
越えない。130℃を越えないのが好ましい。使用する
触媒が五塩化アンチモンの場合、少なくとも100℃の
温度で最良の結果を得ている。使用する触媒が四塩化ス
ズの場合、少なくとも120℃の温度で最良の結果を得
ている。本発明の方法は、液相中で行うのが好ましい。
この場合、反応混合物を液状に維持するように圧力を選
択する。用いる圧力は、反応混合物の温度の関数として
変化する。一般に2 bar〜40 barである。The molar ratio of hydrogen fluoride to chloro (fluoro) butane used is generally at least 4. This action is preferably carried out with a molar ratio of at least 8.
The molar ratio of hydrogen fluoride to chloro (fluoro) butane used generally does not exceed 25. Preferably, the molar ratio should not exceed 18. The temperature at which the hydrofluorination is carried out is generally at least 50 ° C. It is preferably at least 80 ° C. The temperature generally does not exceed 150 ° C. It is preferable not to exceed 130 ° C. When the catalyst used is antimony pentachloride, the best results are obtained at temperatures of at least 100 ° C. When the catalyst used is tin tetrachloride, the best results are obtained at temperatures of at least 120 ° C. The method of the invention is preferably carried out in the liquid phase.
In this case, the pressure is chosen to keep the reaction mixture in the liquid state. The pressure used varies as a function of the temperature of the reaction mixture. Generally from 2 bar to 40 bar.
【0009】本発明の方法は、温度、圧力、及び使用す
る反応体、特にフッ化水素に耐性がある材料からなる、
いかなる反応器においても行うことができる。本発明の
方法は、非連続的又は連続的に行うことができる。後者
(連続的)の場合、反応混合物から得られた生成物を分
離し、他の反応体及び生成物、特に不完全にフッ素化し
たクロロ(フルオロ)ブタンの部分を反応器に再循環さ
せるのがよい。本方法は密閉系又は開放系で行うことが
できる。後者(開放系)の場合、反応混合物から形成さ
れた塩化水素を完全に、又は部分的に抽出するのがよ
い。そのような技術において、例えば、塩化水素と他の
反応物との完全に分離させるために、精留カラムを支持
する蒸留反応器中で本方法を実施することができる。The process according to the invention consists of a material which is resistant to temperature, pressure and the reactants used, in particular hydrogen fluoride.
It can be carried out in any reactor. The method of the present invention can be performed discontinuously or continuously. In the latter case (continuous), the product obtained from the reaction mixture is separated off and the other reactants and products, in particular the part of the incompletely fluorinated chloro (fluoro) butane, are recycled to the reactor. Is good. The method can be performed in a closed system or an open system. In the latter case (open system), the hydrogen chloride formed from the reaction mixture should be completely or partially extracted. In such a technique, the process can be carried out, for example, in a distillation reactor supporting a rectification column for complete separation of hydrogen chloride from other reactants.
【0010】本発明の方法は、一般式CH3-CClx F
2-x - CH2-CCly F3-y (式中、x=0、1、又は
2であり、y=0、1、2、又は3であり、かつx+y
≧1である)のクロロ(フルオロ)ブタンのヒドロフル
オロ化による、1,1,1,3,3-ペンタフルオロブタンの調製
に適用するのがよいことがわかる。本発明の方法のこの
適用において、ヒドロフルオロ化触媒は、周期表 IVa族
及びVa族元素の金属の無機塩(好ましくは塩化物、フッ
化物、及びクロロフルオロ化物である)から選択するの
がよい。1,1,1,3,3-ペンタフルオロブタンの最適な収率
を保証するのに必要なヒドロフルオロ化反応の時間(du
ration)は、作業条件の関数として変化させることがで
き、各々のケースで実験室での試験により評価すること
ができる。ヒドロフルオロ化反応の最後に、製造した1,
1,1,3,3-ペンタフルオロブタンを容易に回収することが
できる。実験室での操作法は、反応体を周囲温度に冷却
し、内容物を水及びテトラクロロエチレンの入った分液
漏斗に移すことからなる。1,1,1,3,3-ペンタフルオロブ
タンを含む有機相を、次に水相、特に未反応フッ化水素
を含む水相から分離する。1,1,1,3,3-ペンタフルオロブ
タンを後に蒸留精製することができる。以下の実施例は
本発明を例示する目的のものであり、いかなる限定をも
含まない。The process of the present invention has the general formula CH 3 --CCl x F
2-x - in CH 2 -CCl y F 3-y ( wherein, x = 0, 1, or a 2, y = 0, 1, 2, or 3, and x + y
It is found to be suitable for the preparation of 1,1,1,3,3-pentafluorobutane by hydrofluorination of chloro (fluoro) butane (≧ 1). In this application of the method of the present invention, the hydrofluorination catalyst may be selected from inorganic salts of metals of groups IVa and Va of the Periodic Table, preferably chlorides, fluorides and chlorofluorides. . The time (du) of the hydrofluorination reaction required to ensure the optimum yield of 1,1,1,3,3-pentafluorobutane (du
ration) can be varied as a function of working conditions and can be evaluated in each case by laboratory tests. At the end of the hydrofluorination reaction
1,1,3,3-Pentafluorobutane can be easily recovered. The laboratory procedure consists of cooling the reactants to ambient temperature and transferring the contents to a separatory funnel containing water and tetrachloroethylene. The organic phase containing 1,1,1,3,3-pentafluorobutane is then separated from the aqueous phase, especially the aqueous phase containing unreacted hydrogen fluoride. 1,1,1,3,3-Pentafluorobutane can be subsequently purified by distillation. The following examples are intended to illustrate the present invention without any limitation.
【0011】[0011]
【実施例1】ハステロイ(登録商標Hastelloy )B2ステ
ンレス鋼からなる 0.5リットル オートクレーブを用
い、撹拌器、温度計プローブ、破裂ディスク(bursting
disc)、試験中行われる液相のサンプリングを可能に
する浸漬管、及び導入すべき反応体注入可能口を備えて
いた。この反応器を予め排気して、−20℃に冷却し、
これにCH3-CF2-CH2-CClF2 73.2重量%並
びに実験式C4 H5 Cl2 F3 の化合物19.2重量
%、並びに1,1-ジクロロ−1-フルオロエタン、トリクロ
ロエタン、及びクロロフルオロ化ヘキサンからなる残り
(7.6重量%)を含む混合物109gを入れた。四塩
化スズ0.036モル及びフッ化水素7.25モルを続
いて、その中に加えた。Example 1 A 0.5 liter autoclave made of Hastelloy B2 stainless steel was used with a stirrer, thermometer probe, bursting disc (bursting).
disc), a dip tube allowing the sampling of the liquid phase to be performed during the test, and a reactant injection port to be introduced. The reactor was previously evacuated and cooled to -20 ° C,
This contained 73.2% by weight of CH 3 —CF 2 —CH 2 —CClF 2 and 19.2% by weight of a compound of the empirical formula C 4 H 5 Cl 2 F 3 , as well as 1,1-dichloro-1-fluoroethane and trichloroethane. And 109 g of a mixture containing chlorofluorinated hexane and the rest (7.6% by weight). 0.036 mol of tin tetrachloride and 7.25 mol of hydrogen fluoride were subsequently added therein.
【0012】反応混合物を撹拌し、その後徐々に100
℃まで加熱し、圧力を20 barにした。100℃で4時
間後、温度を120℃まで上昇させた。定期的に液相中
で行うサンプリングを用いて、ヒドロフルオロ化反応の
進行を追跡した。これらのサンプルをテトラクロロエチ
レンで希釈し、この組成物を気相クロマトグラフィー分
析で測定した。この分析の結果を表1に示す。表1の結
果から、四塩化スズの存在下、120℃で、6時間反応
後、1,1,1,3,3-ペンタフルオロブタンの形成が収率80
%近くまで達したことがわかる。The reaction mixture is stirred and then gradually cooled to 100
Heated to 0 ° C and brought the pressure to 20 bar. After 4 hours at 100 ° C, the temperature was raised to 120 ° C. The progress of the hydrofluorination reaction was followed using periodic sampling in the liquid phase. These samples were diluted with tetrachloroethylene and the composition was determined by gas phase chromatographic analysis. The results of this analysis are shown in Table 1. From the results shown in Table 1, after reacting at 120 ° C. for 6 hours in the presence of tin tetrachloride, the yield of 1,1,1,3,3-pentafluorobutane was 80%.
You can see that it has reached nearly%.
【0013】[0013]
【表1】 ────────────────────────────────── 組成物 % モル/モル C4 (2) 時 間 (1) C4H5Cl2F3 CH3-CF2-CH2-CClF2 CH3-CF2-CH2-CF3 初期混合物 21 79 0 0 11 88 1 0.5 4 93 3 1 2 94 4 2 1 94 5 4 0.5 92 7.5 5.5 0 85 15 6.5 0 70 30 7.5 0 48 52 8.5 0 37.5 62.5 10.5 0 21 79 (1) 反応器中の温度が100℃に達したときを開始時間とした。 (2) モルC4=化合物C4 H5 Cl2 F3 、CH3-CF2-CH2-CClF2 、及 びCH3-CF2-CH2-CF3 のモル分率の合計[Table 1] ────────────────────────────────── Composition% mol / mol C4 (2) time (1) C 4 H 5 Cl 2 F 3 CH 3 -CF 2 -CH 2 -CClF 2 CH 3 -CF 2 -CH 2 -CF 3 initial mixture 21 79 0 0 11 88 1 0.5 4 93 3 1 2 94 4 2 1 94 5 4 0.5 95 92 7.5 5.5 0 85 85 15 6.5 0 70 30 30 7.5 0 48 52 52 8.5 0 37.5 62.5 10.5 0 21 21 79 (1) Reaction The start time was when the temperature in the vessel reached 100 ° C. (2) the total mole C4 = Compound C 4 H 5 Cl 2 F 3 , CH 3 -CF 2 -CH 2 -CClF 2, the mole fraction of及beauty CH 3 -CF 2 -CH 2 -CF 3
【0014】[0014]
【実施例2】手順は、実施例1と同じであった。反応器
を予め排気して、−20℃に冷却し、これにCH3-CF
2-CH2-CClF2 2.4重量%並びに実験式C4 H5
Cl2 F3 の化合物90.3重量%、並びに1,1-ジクロ
ロ−1-フルオロエタン、トリクロロエタン、及びクロロ
フルオロ化ヘキサンからなる残り(7.3重量%)を含
む混合物127gを入れた。五塩化アンチモン0.04
2モル及びフッ化水素8.45モルを続いて、その中に
加えた。反応混合物を撹拌し、その後徐々に100℃ま
で加熱し、圧力を20 barにした。定期的に液相中で行
うサンプリングを用いて、ヒドロフルオロ化反応の進行
を追跡した。これらのサンプルをテトラクロロエチレン
で希釈し、この組成物を気相クロマトグラフィー分析で
測定した。この分析の結果を表2に示す。表2の結果か
ら、五塩化アンチモンの存在下、100℃で、1,1,1,3,
3-ペンタフルオロブタンの形成が速く、6時間反応後、
ほぼ70%の収率となることがわかる。Example 2 The procedure was the same as in Example 1. The reactor was pre-evacuated and cooled to -20 ° C, to which CH 3 -CF
2.4% by weight of 2- CH 2 -CClF 2 and empirical formula C 4 H 5
127 g of a mixture containing 90.3% by weight of the compound of Cl 2 F 3 and the balance (7.3% by weight) consisting of 1,1-dichloro-1-fluoroethane, trichloroethane and chlorofluorinated hexane were introduced. Antimony pentachloride 0.04
2 mol and 8.45 mol hydrogen fluoride were subsequently added therein. The reaction mixture was stirred and then gradually heated to 100 ° C., bringing the pressure to 20 bar. The progress of the hydrofluorination reaction was followed using periodic sampling in the liquid phase. These samples were diluted with tetrachloroethylene and the composition was determined by gas phase chromatographic analysis. The results of this analysis are shown in Table 2. From the results in Table 2, in the presence of antimony pentachloride at 100 ° C, 1,1,1,3,
The formation of 3-pentafluorobutane is fast, and after reacting for 6 hours,
It can be seen that the yield is almost 70%.
【0015】[0015]
【表2】 ────────────────────────────────── 組成物 % モル/モル C4 (2) 時 間 (1) C4H5Cl2F3 CH3-CF2-CH2-CClF2 CH3-CF2-CH2-CF3 初期混合物 97 3 0 0 15 66 19 0.5 <0.5 62 38 1 0 52 48 2 0 43 57 4 0 34 66 6 0 31 69 (1) 反応器中の温度が100℃に達したときを開始時間とした。 (2) モルC4=化合物C4 H5 Cl2 F3 、CH3-CF2-CH2-CClF2 、及 びCH3-CF2-CH2-CF3 のモル分率の合計[Table 2] ────────────────────────────────── Composition% mol / mol C4 (2) time (1) C 4 H 5 Cl 2 F 3 CH 3 -CF 2 -CH 2 -CClF 2 CH 3 -CF 2 -CH 2 -CF 3 initial mixture 97 3 3 0 0 15 66 66 19 0.5 <0.5 62 38 1 0 52 48 2 0 43 57 57 4 0 34 66 66 0 31 69 (1) The start time was when the temperature in the reactor reached 100 ° C. (2) the total mole C4 = Compound C 4 H 5 Cl 2 F 3 , CH 3 -CF 2 -CH 2 -CClF 2, the mole fraction of及beauty CH 3 -CF 2 -CH 2 -CF 3
【0016】[0016]
【実施例3】用いた手順は、実施例2と類似した。反応
器を予め排気して、−20℃に冷却し、これにCH3-C
F2-CH2-CClF2 2.4重量%並びに実験式C4 H
5 Cl2 F3 の化合物90.3重量%、並びに1,1-ジク
ロロ−1-フルオロエタン、トリクロロエタン、及びクロ
ロフルオロ化ヘキサンからなる残り(7.3重量%)を
含む混合物124gを入れた。五塩化アンチモン0.0
41モル及びフッ化水素8.2モルを続いて、その中に
加えた。反応混合物を撹拌し、その後徐々に120℃ま
で加熱し、圧力を20 barにした。クロマトグラフィー
分析の結果を表3に示す。表3の結果から、五塩化アン
チモンの存在下、120℃で、ヒドロフルオロ化反応が
非常に速く、0.5時間反応後、1,1,1,3,3-ペンタフル
オロブタンの収率が90%より大きくなることがわか
る。この反応は、2時間反応後では実質的に完全となる
(99%)。Example 3 The procedure used was similar to Example 2. The reactor was pre-evacuated and cooled to -20 ° C, to which CH 3 -C
2.4% by weight of F 2 —CH 2 —CClF 2 and empirical formula C 4 H
124 g of a mixture containing 90.3% by weight of the compound of 5 Cl 2 F 3 and the balance (7.3% by weight) consisting of 1,1-dichloro-1-fluoroethane, trichloroethane and chlorofluorinated hexane were introduced. Antimony pentachloride 0.0
41 moles and 8.2 moles hydrogen fluoride were subsequently added therein. The reaction mixture was stirred and then gradually heated to 120 ° C., bringing the pressure to 20 bar. The results of the chromatographic analysis are shown in Table 3. From the results of Table 3, the hydrofluorination reaction was very fast at 120 ° C. in the presence of antimony pentachloride, and the reaction yield of 1,1,1,3,3-pentafluorobutane was 0.5 hour after the reaction. It turns out that it becomes larger than 90%. The reaction is essentially complete (99%) after 2 hours of reaction.
【0017】[0017]
【表3】 ────────────────────────────────── 組成物 % モル/モル C4 (2) 時 間 (1) C4H5Cl2F3 CH3-CF2-CH2-CClF2 CH3-CF2-CH2-CF3 初期混合物 97 3 0 0 0 25 75 0.5 0 7 93 1 0 3 97 2 0 1 99 4 0 <0.5 >99.5 (1) 反応器中の温度が120℃に達したときを開始時間とした。 (2) モルC4=化合物C4 H5 Cl2 F3 、CH3-CF2-CH2-CClF2 、及 びCH3-CF2-CH2-CF3 のモル分率の合計[Table 3] ────────────────────────────────── Composition% mol / mol C4 (2) time (1) C 4 H 5 Cl 2 F 3 CH 3 -CF 2 -CH 2 -CClF 2 CH 3 -CF 2 -CH 2 -CF 3 initial mixture 97 3 3 0 0 0 25 25 75 0.5 0 7 9 3 10 3 97 2 0 1 99 4 0 <0.5> 99.5 (1) The time when the temperature in the reactor reached 120 ° C was defined as the start time. (2) the total mole C4 = Compound C 4 H 5 Cl 2 F 3 , CH 3 -CF 2 -CH 2 -CClF 2, the mole fraction of及beauty CH 3 -CF 2 -CH 2 -CF 3
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 FI 技術表示箇所 // C07B 61/00 300 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI technical display location // C07B 61/00 300
Claims (13)
Vb族、及び VIb族元素の金属の誘導体から選ばれる触媒
の存在下でヒドロフルオロ化を行うことを特徴とするフ
ッ化水素による、一般式C4 H5 ClX F5-X (式中、
x=1〜5)のクロロ(フルオロ)ブタンのヒドロフル
オロ化法。1. A periodic table IIIa group, IVa group, IVb group, Va group,
Hydrofluorination is carried out in the presence of a catalyst selected from the group consisting of metal derivatives of the Vb group and the VIb group elements, and the compound of the general formula C 4 H 5 Cl X F 5-X (wherein
Hydrofluorination method of chloro (fluoro) butane of x = 1-5).
の金属の誘導体から選ばれることを特徴とする請求項1
記載の方法。2. The catalyst is selected from the group IVa of the periodic table and a metal derivative of the group Va element.
The method described.
体から選ばれることを特徴とする請求項2記載の方法。3. The method of claim 2, wherein the catalyst is selected from tin and antimony derivatives.
ロロフルオロ化物からから選ばれることを特徴とする請
求項1〜請求項3のいずれか1項記載の方法。4. The method according to claim 1, wherein the catalyst is selected from chlorides, fluorides and chlorofluorides.
とを特徴とする請求項4記載の方法。5. The method of claim 4, wherein the catalyst is antimony pentachloride.
記触媒を0.001〜1モルの比率で用いることを特徴
とする請求項1〜請求項5のいずれか1項記載の方法。6. The process according to claim 1, wherein the catalyst is used in a ratio of 0.001 to 1 mol per mol of chloro (fluoro) butane.
るフッ化水素のモル比が4〜25であることを特徴とす
る請求項1〜請求項6のいずれか1項記載の方法。7. The method according to claim 1, wherein the molar ratio of hydrogen fluoride to chloro (fluoro) butane used is 4 to 25.
温度で行うことを特徴とする請求項1〜請求項7のいず
れか1項に記載の方法。8. The method according to claim 1, wherein the hydrofluorination is carried out at a temperature of 50 ° C. to 150 ° C.
arの液相中で行うことを特徴とする請求項1〜請求項8
のいずれか1項に記載の方法。9. The hydrofluorination is carried out at a pressure of 2 bar to 40 b.
It is performed in the liquid phase of ar.
The method according to any one of claims 1 to 4.
式CH3-CClx F 2-x - CH2-CCly F3-y (式
中、x=0、1、又は2であり、y=0、1、2、又は
3であり、かつx+y≧1である)の化合物から選ばれ
ることを特徴とする請求項1〜請求項9のいずれか1項
記載の方法。10. The chloro (fluoro) butane is generally
Formula CH3-CClxF 2-x-CH2-CClyF3-y(formula
Where x = 0, 1, or 2, and y = 0, 1, 2, or
3 and x + y ≧ 1)
10. Any one of claims 1 to 9 characterized in that
The method described.
3,3-テトラフルオロ−1-クロロブタン、1,3,3-トリフル
オロ−1,1-ジクロロブタン、及び1,1,3-トリフルオロ−
1,3-ジクロロブタンであることを特徴とする請求項10
記載の方法。11. The chloro (fluoro) butane is 1,1,
3,3-tetrafluoro-1-chlorobutane, 1,3,3-trifluoro-1,1-dichlorobutane, and 1,1,3-trifluoro-
11. It is 1,3-dichlorobutane.
The method described.
リデンをフッ化水素と反応させることによって得られる
ことを特徴とする請求項10又は請求項11記載の方
法。12. A process according to claim 10 or 11, characterized in that chloro (fluoro) butane is obtained by reacting vinylidene chloride with hydrogen fluoride.
のための請求項10〜請求項12のいずれか1項記載の
方法の使用。13. Use of the process according to any one of claims 10 to 12 for the preparation of 1,1,1,3,3-pentafluorobutane.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9410684 | 1994-09-05 | ||
FR9410684A FR2724167B1 (en) | 1994-09-05 | 1994-09-05 | PROCESS FOR THE HYDROFLUORINATION OF CHLORO (FLUORO) BUTANE |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2006254053A Division JP2006335770A (en) | 1994-09-05 | 2006-09-20 | Process for hydrofluorination of chloro(fluoro)butane |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0899918A true JPH0899918A (en) | 1996-04-16 |
JP3944254B2 JP3944254B2 (en) | 2007-07-11 |
Family
ID=9466744
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP22349695A Expired - Fee Related JP3944254B2 (en) | 1994-09-05 | 1995-08-31 | Method for hydrofluorination of chloro (fluoro) butane |
JP2006254053A Pending JP2006335770A (en) | 1994-09-05 | 2006-09-20 | Process for hydrofluorination of chloro(fluoro)butane |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2006254053A Pending JP2006335770A (en) | 1994-09-05 | 2006-09-20 | Process for hydrofluorination of chloro(fluoro)butane |
Country Status (12)
Country | Link |
---|---|
US (1) | US5739406A (en) |
EP (1) | EP0699649B1 (en) |
JP (2) | JP3944254B2 (en) |
KR (1) | KR100363940B1 (en) |
AT (1) | ATE186289T1 (en) |
BR (1) | BR9503889A (en) |
CA (1) | CA2157211C (en) |
DE (1) | DE69513111T2 (en) |
DK (1) | DK0699649T3 (en) |
ES (1) | ES2140615T3 (en) |
FR (1) | FR2724167B1 (en) |
TW (1) | TW298589B (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11158088A (en) * | 1997-09-24 | 1999-06-15 | Solvay & Cie | Separation of hydrogen fluoride from mixture of hydrogen fluoride using 3-6c hydrofluoroalkane |
JP2002524431A (en) * | 1998-09-03 | 2002-08-06 | ゾルファイ フルーオル ウント デリヴァーテ ゲゼルシャフト ミット ベシュレンクテル ハフツング | Purification of 1,1,1,3,3-pentafluorobutane |
JP2003511226A (en) * | 1999-10-06 | 2003-03-25 | ソルヴェイ | Method for preparing organic compound and method for recovering cocatalyst |
JP2009203239A (en) * | 1998-12-18 | 2009-09-10 | Solvay (Sa) | Azeotropic composition and method for producing hydrofluoroalkane |
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Publication number | Priority date | Publication date | Assignee | Title |
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FR2724167B1 (en) * | 1994-09-05 | 1996-11-29 | Solvay | PROCESS FOR THE HYDROFLUORINATION OF CHLORO (FLUORO) BUTANE |
GB9518525D0 (en) * | 1995-09-11 | 1995-11-08 | Zeneca Ltd | Novel process |
FR2744442B1 (en) * | 1996-02-01 | 1998-02-27 | Atochem Elf Sa | PREPARATION OF 1,1,1,3,3-PENTACHLOROBUTANE AND 1,1,1,3,3, -PENTAFLUOROBUTANE |
US6075172A (en) * | 1996-09-03 | 2000-06-13 | Zeneca Limited | Chlorofluorohydrocarbon and process thereto |
US6350926B1 (en) | 1996-09-03 | 2002-02-26 | Syngenta Limited | Chlorofluorohydrocarbon and process thereto |
JP2001514645A (en) * | 1997-03-11 | 2001-09-11 | ゼネカ・リミテッド | Fluorination method |
CA2288939A1 (en) * | 1997-05-05 | 1998-11-12 | Solvay (Societe Anonyme) | Method for preparing 1,1,1,3,3-pentachlorobutane |
FR2791976B1 (en) | 1999-03-24 | 2001-07-27 | Solvay | COMPOSITIONS CONTAINING HYDROGEN FLUORIDE AND 1,1,1,3,3-PENTAFLUOROBUTANE, PROCESS FOR THE SEPARATION OF MIXTURES COMPRISING SUCH COMPOSITIONS AND PROCESS FOR THE SYNTHESIS OF 1,1,1,3,3-PENTAFLUOROBUTANE |
US6399841B1 (en) | 1999-03-24 | 2002-06-04 | Solvay (Societe Anonyme) | Method for separating hydrogen fluoride from its mixtures with 1,1,1,3,3-pentafluorobutane and method for making 1,1,1,3,3-pentafluorobutane |
FR2791975B1 (en) * | 1999-03-24 | 2001-07-27 | Solvay | PROCESS FOR SEPARATING HYDROGEN FLUORIDE FROM ITS MIXTURES WITH 1,1,1,3,3-PENTAFLUOROBUTANE AND PROCESS FOR PRODUCING 1,1,1,3,3-PENTAFLUOROBUTANE |
KR100379625B1 (en) * | 2000-08-05 | 2003-04-10 | 주식회사 세종소재 | Getter |
US6518467B2 (en) | 2000-12-29 | 2003-02-11 | Honeywell International Inc. | Method of making hydrofluorocarbons and hydrochlorofluorocarbons |
US6673264B2 (en) | 2001-06-01 | 2004-01-06 | Honeywell International Inc. | Azeotrope-like compositions of 1,1,1,3,3-pentafluorobutane and hydrogen fluoride |
CN102224123B (en) * | 2008-11-25 | 2014-11-26 | 苏威氟有限公司 | Process for the preparation of chlorofluoroalkenes |
EP2196445A1 (en) | 2008-12-15 | 2010-06-16 | Solvay Fluor GmbH | Process for reducing the metal content in organic heavy boiler waste |
TW201103972A (en) | 2009-04-01 | 2011-02-01 | Solvay Fluor Gmbh | Process for the manufacture of etched items |
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---|---|---|---|---|
CA535808A (en) * | 1957-01-15 | A. Wiseman Park | 2,3-difluoro-1,3-butadiene and preparation thereof | |
US2439299A (en) * | 1946-07-26 | 1948-04-06 | Phillips Petroleum Co | Production of halogenated hydrocarbons containing fluorine |
GB675372A (en) * | 1949-01-06 | 1952-07-09 | Firestone Tire & Rubber Co | Improvements in or relating to 2, 3-difluoro-1, 3, butadiene, its polymers and copolymers and the preparation thereof |
US2981762A (en) * | 1957-12-13 | 1961-04-25 | Allied Chem | Manufacture of fluoro butanes |
GB938070A (en) * | 1961-04-05 | 1963-09-25 | Allied Chem | New fluorination process |
LU75857A1 (en) * | 1976-09-22 | 1978-05-12 | ||
BE1005095A3 (en) * | 1991-07-10 | 1993-04-20 | Solvay | PROCESS FOR THE PREPARATION OF 1,1-dichloro-1,3,3,3-tetrafluoropropane. |
BE1005096A3 (en) * | 1991-07-10 | 1993-04-20 | Solvay | PROCESS FOR THE PREPARATION OF 1-chloro-1,1,3,3,3-PENTAFLUOROPROPANE AND 1,1,1,3,3,3-hexafluoropropane. |
JP3605831B2 (en) * | 1992-10-05 | 2004-12-22 | ダイキン工業株式会社 | Method for fluorinating halogenated hydrocarbons |
US5395997A (en) * | 1993-07-29 | 1995-03-07 | Alliedsignal Inc. | Process for the preparation of hydrofluorocarbons having 3 to 7 carbon atoms |
FR2724167B1 (en) * | 1994-09-05 | 1996-11-29 | Solvay | PROCESS FOR THE HYDROFLUORINATION OF CHLORO (FLUORO) BUTANE |
-
1994
- 1994-09-05 FR FR9410684A patent/FR2724167B1/en not_active Expired - Fee Related
-
1995
- 1995-08-29 AT AT95202333T patent/ATE186289T1/en active
- 1995-08-29 DK DK95202333T patent/DK0699649T3/en active
- 1995-08-29 TW TW084109011A patent/TW298589B/zh not_active IP Right Cessation
- 1995-08-29 EP EP95202333A patent/EP0699649B1/en not_active Expired - Lifetime
- 1995-08-29 ES ES95202333T patent/ES2140615T3/en not_active Expired - Lifetime
- 1995-08-29 DE DE69513111T patent/DE69513111T2/en not_active Expired - Lifetime
- 1995-08-30 US US08/520,763 patent/US5739406A/en not_active Expired - Lifetime
- 1995-08-30 CA CA002157211A patent/CA2157211C/en not_active Expired - Fee Related
- 1995-08-31 JP JP22349695A patent/JP3944254B2/en not_active Expired - Fee Related
- 1995-08-31 BR BR9503889A patent/BR9503889A/en not_active IP Right Cessation
- 1995-09-05 KR KR1019950029021A patent/KR100363940B1/en not_active IP Right Cessation
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2006
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11158088A (en) * | 1997-09-24 | 1999-06-15 | Solvay & Cie | Separation of hydrogen fluoride from mixture of hydrogen fluoride using 3-6c hydrofluoroalkane |
JP2002524431A (en) * | 1998-09-03 | 2002-08-06 | ゾルファイ フルーオル ウント デリヴァーテ ゲゼルシャフト ミット ベシュレンクテル ハフツング | Purification of 1,1,1,3,3-pentafluorobutane |
JP2009203239A (en) * | 1998-12-18 | 2009-09-10 | Solvay (Sa) | Azeotropic composition and method for producing hydrofluoroalkane |
JP4785251B2 (en) * | 1998-12-18 | 2011-10-05 | ソルヴェイ(ソシエテ アノニム) | Method for separating mixture containing at least one hydrofluoroalkane and hydrogen fluoride, method for preparing hydrofluoroalkane, and azeotropic composition |
JP2003511226A (en) * | 1999-10-06 | 2003-03-25 | ソルヴェイ | Method for preparing organic compound and method for recovering cocatalyst |
JP4817572B2 (en) * | 1999-10-06 | 2011-11-16 | ソルヴェイ(ソシエテ アノニム) | Preparation method of organic compound and recovery method of promoter |
Also Published As
Publication number | Publication date |
---|---|
KR100363940B1 (en) | 2003-01-29 |
DE69513111D1 (en) | 1999-12-09 |
EP0699649A1 (en) | 1996-03-06 |
CA2157211A1 (en) | 1996-03-06 |
FR2724167B1 (en) | 1996-11-29 |
TW298589B (en) | 1997-02-21 |
CA2157211C (en) | 2007-08-21 |
DE69513111T2 (en) | 2000-08-17 |
US5739406A (en) | 1998-04-14 |
JP2006335770A (en) | 2006-12-14 |
ATE186289T1 (en) | 1999-11-15 |
ES2140615T3 (en) | 2000-03-01 |
DK0699649T3 (en) | 2000-05-08 |
BR9503889A (en) | 1996-09-17 |
FR2724167A1 (en) | 1996-03-08 |
JP3944254B2 (en) | 2007-07-11 |
EP0699649B1 (en) | 1999-11-03 |
KR960010597A (en) | 1996-04-20 |
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